The geometric structures of gas-phase Sr2+ hydrates are calculated quantum chemically by using hybrid (B3LYP) and meta-GGA (TPSS) density functional theory, and a range of thermodynamic data (including sequential bond enthalpies, entropies and free energies for the reactions Sr2+(H2O)n−1+H2O→Sr2+(H2O)n) are shown to be in excellent agreement with experiment. When the number of coordinating water molecules exceeds six, such that water begins to occupy the second solvation shell, it is found that detailed analysis based on both geometrical and conformational entropy is required in order to confidently identify the experimentally observed structures. The significant increase in coordination number observed experimentally between the gas- and aqueous-phase species is successfully reproduced, as is the first solvation shell geometry. Inaccurate second shell geometries imply that larger model systems may be required to achieve agreement with experiment. Candidate species for on-going computational studies of the interaction of hydrated Sr2+ with brucite surfaces have been identified.